JP2602700Y2 - Solid cursive - Google Patents

Description

[Detailed description of the invention]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid cursive type. More specifically, the present invention relates to a solid writing material such as a crayon or a color core that forms a thermochromic handwriting. More specifically, the present invention relates to a solid writing element in which either of the two aspects before and after the discoloration of the handwriting is alternately stored and stored so as to be visible in a normal temperature range.

[0002]

2. Description of the Related Art Japanese Patent Publication No. 51-48085 discloses a solid writing material for forming a thermochromic handwriting.

[0003]

The problem of the present invention is that the above-described thermochromic handwriting by the conventional solid writing material changes color before and after a predetermined temperature, and a specific one of the two states before and after the change at room temperature. Only states can exist. That is, the other state is maintained while the heat or cold required for the state to be applied is applied, but returns to the state exhibited in the normal temperature range if the application of the heat or cold is stopped. As compared with a conventional drawing material that provides non-thermochromic handwriting, the merchantability due to thermochromic discoloration has not been satisfied even if the discoloration is imparted. It is an object of the present invention to provide a solid cursive body that further enhances the merchantability by effectively exhibiting the thermochromic effect.

[0004]

According to the present invention, there is provided a solid writing material for forming a thermochromic hand which is formed by holding and molding a thermochromic pigment in a dispersible wax in a dispersed state, wherein the thermochromic pigment has a temperature. -A quasi-reversible thermosensitive dye which exhibits a large hysteresis characteristic and changes its color in relation to the color density is included, and the particle size is 0 . 5 to 50 μm microcapsule pigment, blended and molded at a ratio of 8 to 35% by weight based on the total amount of solid cursive, and the temperature of the quasi-reversible thermosensitive dye increases in the first hue state. In the process, when the temperature reaches the second temperature t ₃ , the first hue begins to change color, and completely becomes the second hue in a temperature range equal to or higher than the temperature t ₄ higher than the second temperature t ₃ . In the process of decreasing the temperature in the two-hue state, when the temperature reaches the first temperature t ₂ lower than the second temperature t ₃ , the second hue begins to change color, and the temperature t lower than the first temperature t _2. become completely first hue in _{one of} the following temperature range, both phases of the first color and the second color temperature region can be coexistence between the temperature of the first temperature t ₂ and the second temperature t ₃ A temperature-sensitive dye exhibiting hysteresis characteristics, wherein the temperature t ₁ is 0 ° C.
To a temperature between 25 ° C., a temperature range between the first temperature t ₂ and the second temperature t ₃ is at a temperature in the range of 5 ° C. to 40 ° C., the temperature t ₄ is 25 ° C. to 45 A quasi-reversible thermosensitive dye having a temperature between ℃ is selected, and the handwriting is colored or colorless by application of heat or cold, or is colored [A] and colored [B]. 5 ° C to 40
A requirement is a solid cursive writing that can be alternately stored and maintained in a temperature range of ° C.

As the quasi-reversible thermosensitive dye described above, a reversible thermosensitive recording composition previously proposed by the present applicant (Japanese Patent Publication No. 4-17154) can be applied. The quasi-reversible thermosensitive dye exhibits a hysteresis characteristic in the relationship between temperature and color density, and changes color, that is, when the temperature is increased from a temperature lower than the color changing temperature range, and conversely, the temperature is changed from a temperature higher than the color changing temperature range. In this case, the color changes following a different path from the case where the color is lowered. This will be described with reference to FIG. In FIG. 2, the change in the color density due to the temperature change proceeds along the arrow. The point A (temperature t ₁ ) in the graph is a point where the color becomes completely colored at a temperature lower than this, and the point B (temperature t ₃ ) is a substantial discoloration (extinction) in the process of increasing the temperature. The point C (temperature t ₄ ) is a point where the color is completely erased at a higher temperature, and the temperature range between t ₁ and t ₄ is the discoloration temperature range. The first hue and the second hue can coexist, and the temperature range between t ₂ and t ₃ , which is a region where the color density difference is large, is a substantial color change temperature range, that is, the first hue and the second hue. This is a two-color holding temperature range in which hue is held. In the above, t ₁ is a temperature obtained by putting in a refrigerator or a refrigerator filled with ice chips or cold water, that is, a temperature of about 0 ° C. to 25 ° C., and t ₄ is a body temperature, a hair dryer, hot water or the like. The temperature obtained by the filled heater or the like, that is, about 25 ° C. to 4
It indicates a temperature of 5 ° C., and the above-mentioned 5 ° C. to 40 ° C.
Within the range, more preferably within the range of 10 ° C. to 35 ° C., the handwriting before and after the change can be alternately stored and stored. Note that the first hue and the second hue are effective if they have a color-colorless relation or a color [A] -color [B] relation, and the state of the color [A] or the color [B] is effective. Can be obtained by using a non-color-changing pigment (general pigment) together with the quasi-reversible thermosensitive dye.

The quasi-reversible thermosensitive dye is applied as a microcapsule pigment encapsulated in a microcapsule in order to protect the thermosensitive dye, maintain the same composition under various conditions, and provide the same effect. Is done. The microencapsulation pigmentation is performed by a known microencapsulation method, that is, an interfacial polymerization method, an interfacial polycondensation method, an in-situ polymerization method, a curing-in-liquid coating method, a phase separation method from an aqueous solution, a spray drying method, or the like, or The interfacial polymerization method and the in-situ polymerization method are particularly effective. The particle size of the microcapsules is 0.5-50 μm, more preferably 2-30 μm
Within the above-mentioned particle size range, good dispersibility in the formable wax is obtained, and both the color density and the writing feeling are satisfied.
In a system with a particle size exceeding 50 μm, the writing feeling is impaired,
Generates variation in handwriting density.

As the excipient, waxes conventionally used are effective, and specific examples thereof include paraffin wax having a melting point of 40 to 120 ° C., microcrystalline wax, petrolactam, oxidized paraffin wax, and petrolactam oxide. Petroleum wax. Synthetic waxes such as oxidized polyethylene wax, montanic acid wax, ethylene vinyl acetate copolymer wax, ethylene acrylic copolymer wax, vinyl ether wax and the like. Animal and plant waxes such as shellac, carnauba wax, caster wax, and tallow hardened oil. Behenyl behenate, stearyl bebenate, stearyl palmitate, stearyl myristate, stearyl laurate, stearyl stearate, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, stearone, behenic acid, stearic acid, palmitic acid, myristic acid Acids, lauric acid, lignomorinic acid, esters such as cerotic acid, higher alcohols, ketones, fatty acids and the like, palm oil, liquid paraffin, polybutene, polybutadiene, fatty acid fatty acids such as polystyrene oligomers, liquid hydrocarbons, etc. Used together.

[0008]

The quasi-reversible thermosensitive dye having a color change characteristic as exemplified in FIG. 2 has a color change temperature range in the temperature range between t ₁ and t ₄ , and both the first hue and the second hue can coexist. , temperature range of between t ₂ and t ₃ is a region having a large difference in color density substantially discoloration temperature region, i.e., the first hue and the second hue function as two-color holding temperature range to be retained. The two-color holding temperature range is 5
C. to 40.degree. C. (more preferably 10 to 35.degree. C.), and the first hue and the second hue are stored alternately in a normal temperature range. Therefore, the thermal handwriting changed at t ₁ or less, t ₄
The heating handwriting changed as described above functions as a thermochromic solid handwriting that forms a two-sided handwriting that is arbitrarily selected by the user and stored and stored in the normal temperature range. Here, since the quasi-reversible thermosensitive dye is encapsulated in a microcapsule and protected, the same discoloration function is permanently expressed, and an appropriate amount of the microcapsule pigment is appropriately dispersed.
It provides a suitable writing feeling and a thermochromic handwriting without variation.

[0009]

EXAMPLES Example 1 35 parts of paraffin wax 140F (melting point 61 ° C.) [manufactured by Nippon Seiwa Co., Ltd.], 25 parts of ethylene vinyl acetate copolymer wax [manufactured by Nippon Seiwa Co., Ltd.], extremely hardened tallow oil [ Shin Nihon Rika Co., Ltd.] 25 parts by weight of a shaping wax consisting of 1 part of 1,2-benz-6-diethylaminofluoran, 2 parts of bisphenol A and 20 parts of benzyl stearate separately prepared. 15 parts of a microcapsule pigment of an epoxy resin film containing a quasi-reversible thermosensitive dye having a composition was added, mixed with heat, melted, poured into a crayon molding die and cooled to obtain a thermochromic crayon. The parts in the above examples indicate parts by weight, and the same applies to the following examples.
The handwriting written with the crayon shows a pink color when cooled to 18 ° C. or less, becomes colorless at 42 ° C. or more, and in a temperature range of 19 ° C. to 40 ° C., the pink handwriting can be stored and held for visualization. At the same time, colorless handwriting, that is, handwriting in an invisible state could be stored and retained.
The above-mentioned appearance change could be repeatedly reproduced.

Example 2 Paraffin wax 115F (melting point 46 ° C.) (manufactured by Nippon Seiro Co., Ltd.) 5 parts, paraffin wax 140F 25 parts,
In a wax composition comprising 20 parts of ethylene vinyl acetate copolymer wax and 25 parts of stearic acid, a fluorescent pigment Epocolor FP-1007 (fluorescent pink) [manufactured by Nippon Shokubai Co., Ltd.]
5 parts, separately prepared 3-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide 1 part, bisphenol A 2 parts, weight of heptyl stearate 20 parts 20 parts of a microcapsule pigment composed of an epoxy resin film containing a quasi-reversible temperature-sensitive dye having a composition having the same ratio were added, mixed by heating, melted, poured into a crayon molding die, and cooled to obtain a thermochromic crayon. The handwriting written with this crayon is 15
℃ below purple, pink at 30 ° C, 16 ° C
In the temperature range from to 29 ° C., pink and purple colors were alternately stored and stored, and visualization was possible. The present invention is not limited to the crayon of the above-described embodiment, but is also effective in the case where the outer surface is coated and extruded into a color core, and a conventional non-thermochromic solid writing body is continuously provided at the other end. The configuration may be as follows.

[0011]

As described in the above embodiment, the solid writing device of the present invention not only gives a handwriting whose color is changed by a temperature change, but also can be applied with heat or cold required to develop the state. Even in the state where the handwriting disappears, a two-sided handwriting is provided which allows one of the two aspects before and after the change to be stored and held alternately and stored and held in a normal temperature range to be visually recognized. That is, the handwriting formed by one cursive type is made to appear as handwritings of different colors by daily temperature means, and furthermore, the displayed handwriting is arbitrarily selected by the user and stored and stored in the normal temperature range, Moreover, it is possible to provide a solid cursive type that can be repeatedly reproduced and enjoyed. Furthermore, the discoloration effect can be effectively exhibited by using in combination with the conventional non-thermochromic solid writing material.

[Brief description of the drawings]

FIG. 1 is a perspective view of one embodiment of a solid cursive body of the present invention.

FIG. 2 is a graph illustrating the relationship between color density and temperature of a quasi-reversible thermosensitive dye.

[Explanation of symbols]

 1 solid cursive

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 11/00-13/00 C09K 9/00-9/02

Claims (1)

(57) [Scope of request for utility model registration] 1. A solid writing material which forms a thermochromic handwriting by holding and molding a thermochromic pigment in a dispersible state in a shape-forming wax, wherein the thermochromic pigment has a large temperature-color density relationship. A quasi-reversible thermosensitive dye which exhibits a hysteresis property and changes color is included, and has a particle size of 0.1 . It is a microcapsule pigment of 5 to 50 μm, and 8 to 30 in the total amount of solid cursive.
Is molded are blended at a ratio of weight percent, the quasi-reversible temperature-sensitive dye in the process of temperature In the first color state is increased and reaches the second temperature t _3, the first color is discolored At first, the second hue is completely obtained in a temperature range equal to or higher than the temperature t ₄ higher than the second temperature t ₃ , and in the process in which the temperature-sensitive dye is in the second hue state and the temperature decreases, the second temperature t 2 _When the first temperature t ₂ lower than ₃ is reached, the second hue begins to change color, and completely becomes the first hue in a temperature range equal to or lower than the temperature t ₁ lower than the first temperature t ₂ and becomes the first hue. ₂ and a temperature-sensitive dye exhibiting hysteresis characteristics both phases can coexist in the first color and the second color in the temperature range between the second temperature of the temperature t _3, wherein said temperature t ₁ is 0 ℃ to a temperature between 25 ° C., a temperature range between the first temperature t ₂ and the second temperature t ₃ is in the range of 5 ° C. to 40 ° C. temperature , And the temperature t ₄ is 25
A quasi-reversible thermosensitive dye having a temperature of between 45 ° C. and 45 ° C. is selected, and the handwriting is colored or colorless by applying heat or cold, or colored [A] and colored [B]. The solid writing body is configured to be able to store data alternately in the temperature range of 5 ° C. to 40 ° C.